This paper showed simple and effective synthesis of copper nanoparticles within controlled diameter using direct electroless deposition on glass substrates, following the sensitization and activation steps. Electroless-deposited metals, such as Cu, Co, Ni, and Ag, and their alloys had many advantages in micro- and nanotechnologies. The structural, morphological, and optical properties of copper deposits were characterized using X-ray diffraction (XRD), atomic force microscopy (AFM), and UV-Vis spectroscopy. The structural data was further analyzed using the Rietveld refinement program. Structural studies reveal that the deposited copper prefers a (111) orientation. AFM studies suggest the deposited materials form compact, uniform, and nanocrystalline phases with a high tendency to self-organize. The data show that the particle size can be controlled by controlling the activator concentration. The absorption spectra of the as-deposited copper nanoparticles reveal that the plasmonic peak broadens and exhibits a blue shift with decreasing particle size.